Treatment of hydrocarbons



` Patented Jan. 14, 1941 UNITED STATES TREATMENT oF mnocannoNs Leonard -N. Leum, Bywoocl,l and Edwin R. Birkhimer, Philadelphia, Pa., assignors to The Atlantic Refining Company, Philadelphia, Pa.,v

.a corporation of Pennsylvania e Application March 11', 1940, Serial No. 323,?88 7 Claims. (Cl. 19t-50) The present invention relates to the treatment of hydrocarbons for the purpose of producing therefrom an improved type of motor fuel. In its more speciilc aspects, the present invention re- 5 lates to the'treatment of hydrocarbons of the gasoline type to convert the same into gasoline having improved anti-knock qualities.

In accordance with the present invention, gas- `oline distillates having a boiling range of the l order of 100 F. to`400 F., or heavy vnaphthas 'commonly designated as reformer stocks, are

subjected t0 a reforming treatment for the improvement of the anti-knock qualities thereof. Such treatment comprises essentially a thermal l reforming operation wherein the hydrocarbon distillate is brought into contact, at elevated temperatures, with' a reforming catalyst in the presence of added quantities of sulfur dioxide for a period of time sufficient to increase the anti-knock value of the distillate to a substantial extent. The thermal treatment may be ef fcted at temperatures of from about 750 F. to about 12007 F., and vpreferably at from about 900 F. to about 1000 F. Reforming catalysts 2 5 of the nature of adsorbent earths, such as iullersv earth, are preferred', although other agents such as acid activated clays, bentonite, bauxite, silica gel, synthetic silicates, and the like may be utilized. The quantity of sulfur dioxide employed 80 may vary from about 0.5%- to about 25% by weight of the hydrocarbon distillate, the preferred amount being from about 6%. to about 12% by weight. The'improved distillate from the reforming operation may bererun and/or otherwise treated to. obtain a motor fuel of desired boiling range having a substantially reduced content of sulfur compounds, gum-forming constit-l uents,and the like.

Our invention may be further understood with so reference to the accompanying drawing, which represents diagrammatically a system suitable for` earth. The operating pressure within the heat? ing coil 4 and the catalytic tower l may vary from slightly superatmospheric up to pressures of the polymers. resulting from the catalytic treatment.

order of 3000 lbs/sq. in. The heated mixture is passed through the catalyst bed at a temperature of thel order of 1000 F., and reforming of the distillate therein takes place. As a result of the reforming reaction, molecular rearrangement of 5 the hydrocarbons comprising the distillate occurs, with the evolution of gases including HzS and water vapors. The mixture resulting from the reforming reaction, including'reformed distillate, unrea'cted SO2, and byproducts of the reaction is withdrawn from the bottom of tower land passed through valve-controlled pipe 9 into frac. tionating column I0, wherein the distillate may be separated from small amounts of high boiling l5 Such polymers may be removed from the bottoml of column I0 by means of valve-controlled pipe Il, while the reformed hydrocarbon distillate of desired boiling range and gaseous reaction products may be withdrawn from the top of the col- 20 umn i0 in a vaporous state. The vapors and gases may be conducted by valve-controlled pipe l2 and pipe I3 tocondenser I6 wherein the hydrocarbon vapors are condensed, and the liquid condensate and uncondensed gases are passed by pipe I5 into separator I6. In separator i6 the condensate, i. e., theV reformed hydrocarbon distillate, is separated from the uncondensed gases `and is withdrawn therefrom by means oi* valve-controlled pipe Il. Such reformed distillate maybe treated for the removal of acid gases such asHzS or SO2 by neutralization with caustic soda solution and water washing, the resulting distillate being a motor fuel of improved anti-knock value.

The uncondensed gases accumulating in the upper portion of separator i0 may be vented by means of valve-controlled pipe i8, or' may be recirculated to the thermal reforming system by one or both of the following procedures. yOr, a portion of the gases may be vented and the remainder may be recirculated. 'Uncondensed gases may be withdrawn from thetop of separator i6 through pipe i8 and passedl by valve-controlled pipe 2 0 to the inlet side of pump 3 for `recirculation through the heating coil. Or, the uncondensed gases may be passed through pipe i0 and valve-controlled pipe 2| to pump 22, and forced 'thereby through valve-controlled pipe 23 into pipe 6 carrying heated hydrocarbon distillate from coil 4 to catalytic tower l. If desired, we may introduce untreated distillate from valve-controlled pipe I'into the heating coil i wlthoutsimultaneous introduction of SO2 through valve-controlled pipe 2. In this case we may supply SO2 through -valve-controlled pipe 24, pump 22, and valve-controlled pipe 23 to the heated distillate passing through pipe to the catalyst tower 1.

In the above operation, wehave described the use of fractionating column I0 for separating high catalyst atj a temperature within the range of from about 750 F. to about 1200' F. f 2. 'I'he method of reforming petroleum distillate comprising hydrocarbons boiling substan- 75 ence of added sulfur dioxide,with a reforming I 5 boiling polymers from the reformed distillate. As tially within the gasoline boiling range to improve an alternative procedure, we may eliminate the the anti-knock quality thereof, which comprises use of column I0, and by-pass the heated, re'- intimately contacting said distillate, in the presformed distillate and gases through valve-conence of added sulfur dioxide, withv a reforming v trolled pipe 25, and pipe Il to condenser Il, and catalystat a temperature within the range of thereafter separate the condensed distillate from from about750 'F. to about 1200 F., and sepathe uncondensed gases in separator l0. In this rating from the treated distillate a gasoline fraccase `the condensate removed from thev separator tion of improved anti-knock quality. 1

through valve-controlled pipe I1 may .be neu- 3. 'I'he method of reforming petroleum distiltralized and washed to remove acid gases and sullate comprising hydrocarbons boiling substanfur compounds, and may thereafter be rerun in .tially within the gasulme boiling range to 1m- Suitable diStiHatiOn equipment t0 remove high prove the anti-knock quality thereoffwhich comboiling polymers and produce a motor fuel of prises intimately contacting" said distillate, in Proper boiling range ,8nd imDrOVed anti-knck the presence of from about'0.5.% to about"25% quality. by weight of sulfur dioxide, with a reforming Our invention may be further illustrated 'by catalyst at a temperature within the range of the following examples, which include runs made from about 750 F. to about 1200 F. with fullers earth and S02, fullers earth with- 4. The method of reforming petroleum distilout SO2, and SO: without.i fullers earth. The late comprising hydrocarbons Vboiling substanhydrocarbon distillate employed had a boiling tially within the gasoline boiling range to im- I range of 120 F. to 335 F., an A. P. I. gravity of prove the anti-knock quality thereof, which com- 59;8, an anti-knock or octane value of 57, and prises intimately contacting said distillate, in the a sulfur content of 0.057%. The treatment compresence of from about 0.5%`to about 25% by prised vaporizing the untreated distillate, passweight of sulfur dioxide, with an argillaceous v ing the vapors at substantially atmospheric presreforming catalyst at a temperature within the sure througha bed of 4-8 mesh fullers earth Vrange of from about '150 F. to about 1200 F.

" maintained at a temperature of the order of 5. The method of reforming petroleum distil- 990 F. to 1000 F., condensing th vapors, washlate comprising hydrocarbons -boiling substaning the raw condensate with caustic soda solutially within the gasoline boiling range' to imtion and with water, and thereafter rerunning prove the anti-knock quality thereof, which comthe raw condensate, without fractionation, to prises intimately contacting said distillates, in produce a nished gasoline having a 320 F. disthe presence of-from about 0.5% to about 25% tillation end point. by weight of sulfur dioxide, with fullers earth 401 Treatment v'Treated distillate weight Temp., conm Yield 21d Octane Percent Catalyst pe'ft. F. (raw) eadmpoilnb value sulfur Pm'enz- Pmmc 1000 2.8 0&0 01.0 51 '0.054 005 2.0 01.0 05.0 5s 0.013 00o 3.0 000 04.0 s 01 0.014 1000 2.0 00.0 seo 03.5 0.020 000 as 80.0 85.0 04.5 0.038 000 a1 78.0 v5.0 51.5 0.005 000 2.0 '15.0 710 50.5 0.110

at a.temperature within the range of from about 750 F. to about 1200 F.

6. The method of reforming petroleum distilfullers earth, per se. tially within the gasoline boiling range to im- While, hereinabove, We have shown the treatprove the anti-knock quality thereof, which comment of a relatively light gasoline distillate, it prises intimately contacting said distillate. in the is to be understood that our invention'is equally presence of from about 6% to about 12% by well adapted to the treatment of higher boiling weight of sulfur dioxide, with fullers earth at. gasoline distillates or naphthas having distillaa temperature within the range of from about tion end points up to about 450 F. The hydrof 900 F. to about 1000 F. 4 carbon dlstillates we prefer to treat comprise 7. The method of reforming petroleum distilhydrocarbons boiling Asubstantially within the late' comprisingxhydrocarbons boiling substangasoline boiling range, i. e., from about 100 F. tially within the gasolineboiling range to imto about 400 F., and which may be produced. prove the anti-knock quality thereof, which by distillation, cracking, hydrogenation, polycomprises intimately contacting said distillate, `merization, or alwlation of petroleum hydroin the presence of from vabout 6% to about 12% A, carbons. Y by weight of sulfur-dioxide, with fullers earth What we claim is: at a temperature within the range of from about 1. The method, of reforming petroleum dlstil- 900 F. to about 1000 F., and separating from late comprising 'hydrocarbons boiling substantially within the gasoline boiling range to improve the anti-knock quality thereof. which comprises intimately contacting said distillate, in the. presthe treated distillate a gasoline fraction of improved anti-knock quality.

late comprising hydrocarbons boiling substan- 

